JPH0543903A - Method for granular body coating and method for composite plating by magnetic metal coating - Google Patents

Abstract

PURPOSE:To perform composite plating with uniform film thickness by a simple operation by coating the surface of granular material dispersed on a boat and stuck by drying a binder with magnetic material metal by dry plating before removing the binder. CONSTITUTION:After a binder, such as acrylic clear coating material 2 and starch is applied to a boat 1 for vapor deposition and granular material, such as SiC powder 3 is uniformly dispersed and leveling is performed, the coating material 2 is dried. After that, by dry plating, such as vacuum evaporation with a vacuum evaporation device 4 and sputtering, magnetic material metal, such as iron, Ni is vapor-deposited on the surface of the powder 3, the coating material is dissolved and removed with organic solvent before drying. And SiC powder a part of whose surface is coated with iron, etc., is obtained. Next, the powder is arranged on a magnetic material metal base material 6, such as a magnetized iron plate to plate it and a plating film 7 of Ni, etc., is applied. Besides, the boat 1 may hold powder 3 and dry plating may be performed while oscillating the boat 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coating a granular material with a magnetic metal and a composite plating method using a granular material coated with a magnetic metal.

[0002]

2. Description of the Related Art Composite plating is carried out in order to impart wear resistance and other properties to a substrate, and examples of the substrate to be used include shafts and bearings which require lubricity and polishing tools. Such a composite plating layer is a conventional plating solution that is vigorously stirred to uniformly suspend particles of alumina, diamond, polytetrafluoroethylene, etc. in the plating solution, while The method of eutectoid was used.

[0003]

However, in the above-mentioned composite plating method, it is difficult to control the eutectoid amount of the particles even if the stirring is sufficiently performed, and the plating film thickness becomes uneven. I tended to. Therefore, tools, shafts, bearings, etc., which require precise dimensional accuracy, need to be over-plated, and a step of cutting off an excessively plated portion is required to adjust the dimensions after plating, resulting in a troublesome process. Further, there are drawbacks such that it is difficult to co-deposit large-diameter particles that are hard to float, a large amount of particles are lost, and the plating solution is contaminated with the particles.

An object of the present invention is to perform composite plating with a simpler operation and a uniform film thickness.

[0005]

As a result of intensive studies to solve the above problems associated with composite plating, the present inventor produced a granular body coated with a magnetic metal and used the granular body. The present invention has been completed by finding that the composite plating with a uniform film thickness can be performed by a simple operation.

That is, according to the present invention, after the granular material is sprayed and fixed on the boat to which the adhesive is applied, the adhesive is dried, and at least a part of the surface of the granular material is coated with the magnetic metal by dry plating. It is intended to provide a method for coating a granular material, which is characterized by removing a fixing agent.

The present invention also provides a method for coating a granular material, characterized in that the granular material is housed in a boat and the magnetic metal is coated on the granular material by dry plating while rocking the boat. is there.

Further, the present invention provides a composite plating method characterized in that a granular material having at least a part of its surface coated with a magnetic metal is placed on a magnetic metal substrate and plated. ..

Furthermore, the present invention provides a composite plating method characterized in that a granular material coated with a magnetic metal is arranged and plated on a magnetic metal substrate.

The fixing agent used in the present invention may be any one that is soluble in water or an organic solvent, and examples thereof include acrylic clear paint, acrylic resin, starch, and the like. It is carried out by dissolving the fixing agent with soluble water or an organic solvent.

The granular materials used in the present invention include, for example, resins such as polytetrafluoroethylene, polystyrene, acrylic, tungsten carbide, silicon carbide, organic or inorganic metal compounds such as alumina, and boron nitride, Examples include diamond, carbon, silicon and the like. The particle size of the granules is usually 0.2 μm to 1 mm, preferably 1 μm to 200 μm. The particle size of the non-spherical particles is a value when converted into spherical particles.

The drying of the adhesive of the present invention may be such that the solvent contained in the adhesive does not interfere with the subsequent coating step.

To disperse the granules on the boat to which the fixing agent is applied, it is usually preferable to disperse the granules on the boat and then level the granules.

The magnetic metal used in the present invention includes:
Iron, nickel, cobalt and alloys thereof may be mentioned, as long as the coating layer formed on the granular material has sufficient magnetism to hold the granular material on the magnetic metal substrate.
It may contain components such as other metals.

The coating of the magnetic metal with the granular material according to the present invention is performed by dry plating. In the present invention, dry plating includes vacuum vapor deposition method, sputtering method, ion plating method, etc., vacuum vapor deposition method and sputtering method are preferable for coating a single substance, and sputtering method, ion plating for coating alloy. Method is preferred. The granular material coated with the magnetic metal used in the composite plating method of the present invention is
You may use what was obtained by wet plating.

The thickness of the coating film formed by the above dry plating is not particularly limited, but is preferably about 0.01 to 3 μm.

To coat at least a part of the surface of the granular material with a magnetic metal means to coat a part or all of the surface of the granular material except the part where the granular material and the boat are in contact with each other. To do. The step of fixing the particles on a boat and performing vacuum deposition is illustrated in FIG. 1, and usually, as shown in FIG. 2, a portion of the surface of the particles facing the coating direction is coated with a magnetizing metal. ..

Examples of the magnetic metal base material used in the present invention include iron, nickel, cobalt and alloys containing these. Iron, non-magnetic base materials such as plastics, ceramics, copper, aluminum, stainless steel, etc. The surface may be magnetized by coating a metal having magnetism such as nickel, cobalt and alloys thereof. When the surface of a non-magnetic base material is coated with a magnetic metal, when the non-magnetic base material is a metal, the magnetic metal can be directly coated by electrolytic plating, but the non-magnetic base material is a non-conductive material such as plastic. In this case, first, an electroless plating layer is formed by a conventional method, and then a magnetic metal such as iron, cobalt or nickel is coated by electrolytic plating.

When the granular metal is coated with the magnetic metal by dry plating while rocking the boat, the entire surface of the granular body may be covered with the magnetic metal, and a part of the surface of the granular body is covered with the magnetic metal. It may be covered. Further, the swing may be a movement having a short amplitude such as a vibration, or may be a movement having a longer amplitude.

The granular material coated with the magnetic metal coating according to the method of the present invention, in the case where the metal is iron, is particularly suitable for preventing the coating from dropping during activation by air oxidation and acid treatment before plating. In order to avoid it, you may coat a protective film further with a resin coat.

When the coated particles are arranged on the magnetic metal base material, it is preferable to carry out a leveling operation so that the particles on the magnetic metal base material are uniformly arranged.

The magnetic metal base material on which the coated granular material is arranged is then subjected to a plating process.

In the present invention, a commonly used plating method such as electrolytic plating or electroless plating is used as the plating method for arranging the granular material coated with the magnetic metal on the magnetic metal. The plating conditions and plating composition include the following, for example.

Copper bromide plating solution composition Cuprous bromide 60 g / l Sodium bromide 70 g / l Potassium hydroxide 10 g / l Plating temperature: 55 ° C. Nickel sulphate composition (pH 4.4) Nickel sulfate 270 g / l Nickel chloride 50g / liter Boric acid 40g / liter Plating temperature: 50 ° C Nickel sulfamate composition (pH 4.0) 400g / liter Nickel sulfamate Boric acid 30g / liter Nickel chloride 5g / liter Plating temperature: 50 ° C Chromium plating liquid Composition Chromic anhydride 250 g / l Sulfuric acid 2.5 g / l Trivalent chromium 3 g / l Plating temperature: 50 ° C. Copper sulfate plating solution Composition Copper sulfate pentahydrate 200 g / l Sulfuric acid 50 g / l Plating temperature: 20 ° C. Electroless nickel plating Liquid and electroless copper Kkieki used the following commercially available products. Electroless nickel plating solution Nuron Y-45 (trade name, made by Okuno Pharmaceutical Co., Ltd.) Plating temperature: 90 ° C. Electroless copper plating solution OPC Carper T (trade name, made by Okuno Pharmaceutical Co., Ltd.) Plating temperature: 55 ° C. The state after plating with the liquid is
This is as shown in FIGS. 3 and 4. That is, the particles are arranged almost uniformly on the magnetic metal base material in a state where the magnetic metal coating is brought into contact with the base material, and the plating coating having a constant thickness is coated. The thickness of the plating film can be changed depending on the plating time, and in order to exert the properties of the granular material, it is preferable that the tip of the granular material projects outside the plating film.

In the method of coating a granular material of the present invention, even if a granular material not coated with the magnetic metal is generated, this does not adhere to the magnetic metal base material, so that the magnetic metal is coated. Since it can be easily removed from the granular material, there is no problem.

[0026]

According to the coating method and the composite plating method of the present invention, the plating step is carried out while the particles to be codeposited are held in advance on the surface of the substrate by the magnetic force. The effect can be achieved.

I Unlike the conventional composite plating, strict conditions such as strong stirring are not required, and the composite plating can be formed under normal plating bath and plating conditions.

II Since the granular materials are arranged substantially flat on the magnetic metal base material, the thickness of the plating can be easily controlled by adjusting the thickness of the granular material layer.
In order to match the dimensions even with a base material that requires precise dimensional accuracy, a step of cutting an excessively plated portion after plating is not required, and the plating step can be simplified as a whole. Further, it is possible to easily fix the large-diameter granular material, which has been difficult to stir by the conventional method.

III Not only is the coated granular material economical for use in composite plating, but also the plating solution is not polluted because it is not necessary to add the granular material to the plating solution.

[0030]

EXAMPLES The present invention will be described in more detail below with reference to examples.

The plating solution composition and plating conditions used in the following examples were as described above.

[0032]

Example 1 Acrylic clear paint (2) was applied to a boat (1) for vapor deposition, silicon carbide powder (3) having an average particle size of about 5 μm was evenly dispersed, leveled, and after the adhesive was dried. , Using the vapor deposition device (4), about 0.0
It was vacuum-deposited with a film thickness of 5μ. The state after vapor deposition is as shown in FIG. Next, the acrylic clear paint was dissolved and removed with methyl ethyl ketone (MEK), and dried to obtain a silicon carbide powder whose surface was partially coated with iron.

A magnetized iron plate is used as the magnetic metal base material (6), and the above-mentioned coated silicon carbide powder is sprinkled on the iron plate and leveled to give 1 g / dm ² of the carbide powder. It was arranged uniformly. The arranged silicon carbide powder (3) is arranged with the iron coating film (5) facing the surface of the magnetized iron plate (6) as shown in FIG. The magnetized iron plate (6) on which the silicon carbide powder was uniformly arranged was nickel-plated using the above-mentioned first nickel plating solution.

In the obtained plated composite of iron plate, the nickel plating film (7) becomes constant near the upper ends of the particles (3) as shown in FIGS. That is, the film thickness is about 100
It was confirmed that the method of the present invention using a granular material having a part of the surface coated with a magnetized metal is an excellent composite plating method, as it is almost constant in μm and the fixing of the plating is good.

[0035]

Example 2 A water-soluble acrylic clear paint was applied to a boat for vapor deposition, and in a semi-dried state, diamond (3) having an average particle diameter of about 10 μm was uniformly dispersed, leveled, and then completely dried. An iron-nickel alloy was vapor-deposited to a film thickness of about 0.3 μm, and the acrylic clear paint was removed with a weak alkaline aqueous solution at 60 ° C. to prepare a magnetic metal-coated diamond powder. A magnetized iron plate was used as a magnetic metal base material, the above diamond powder was sprayed, and then leveling was performed to uniformly arrange the diamond powder at a rate of 0.2 g / dm ² . Electroless nickel plating was performed on the magnetized iron plate on which the diamond powder was uniformly arranged.

The obtained plated composite of iron plate had a film thickness of about 15 μm, which was almost constant, had a good grinding effect, and had good fixing of the plating.

[0037]

Example 3 Teflon powder having a particle size of 5 to 15 μm was placed in a vapor deposition boat equipped with a vibrator, and cobalt was vapor deposited on the entire Teflon powder while rocking the boat. As the magnetic metal base material, a copper plate plated with about 5 μm of electric nickel and then magnetized with nickel was used.

On a copper plate coated with nickel, Teflon powder coated entirely with cobalt was uniformly arranged at a rate of 0.3 g / dm ² by leveling, and electro nickel plating was performed under the same conditions as in Example 1. ..

The composite plated body of the obtained copper plate had a film thickness of about 20 μm and was substantially constant, the plating was well fixed, and the abrasion resistance and self-lubrication were good. It was confirmed that a good composite plated body could be obtained.

[0040]

Example 4 In the same manner as in Example 3, a diamond powder having a particle diameter of about 5 μm and having nickel deposited on the entire surface of the diamond powder was prepared. The aluminum base material was treated with zincate and then electro-nickel plated, and then nickel was magnetized to obtain a magnetic metal base material. Nickel deposited diamond powder was sprayed on this base material, leveled and arranged at a rate of 0.1 g / dm ² , and then chromium plating was performed using the above chromium plating solution.

The composite plated body of the obtained aluminum plate had a film thickness of about 5 μm, was substantially constant, and had a very high hardness surface layer.

[0042]

[Example 5] In the same manner as in Example 3, the particle size was about 0.5-.
A boron nitride powder was prepared by depositing an iron-cobalt alloy by sputtering on the entire surface of the 1 μm boron nitride powder.

The magnetic metal base material was prepared as follows.

That is, an acrylonitrile-butadiene-styrene resin (ABS resin) was subjected to etching, catalyst, pretreatment with an accelerator and chemical nickel in this order, and then iron plating was performed to magnetize the iron. The magnetic metal base material was used. The boron nitride powder is sprinkled on the base material and leveled to 0.5.
After arranging at a ratio of g / dm ² , a plating operation was performed using a second nickel plating solution.

The obtained ABS resin composite plated body had a film thickness of about 20 μm, and the fixing of the plating was good.

From the above results, the method of the present invention is
It was shown that it can be applied to resins.

[0047]

Example 6 The particle size is 100 to 2 in the same manner as in Example 3.
A diamond powder was prepared by vacuum-depositing iron on the entire surface of the 00 μm diamond powder. As the magnetic metal base material, a magnetized iron plate was used. The iron powder is sprayed with the above diamond powder and leveled to 1 g /
After arranging at a ratio of dm ² , a plating operation was performed using a second nickel plating solution to produce a rough polishing grindstone in which diamond particles were deposited.

The composite plated body of the obtained substrate has a film thickness of about 5
It was almost constant at 0 μm.

Such a grindstone containing a large number of diamond particles is difficult to manufacture by the conventional composite plating method, and the usefulness of the present invention is shown also from this point.

Even when an electroless nickel plating solution (Nuron Y-45 (trade name, manufactured by Okuno Chemical Industries Co., Ltd.)) was used instead of the second nickel plating solution, the same excellent effect was obtained.

[0051]

Example 7 In addition to using Teflon powder having a particle size of 5 to 15 μm coated with cobalt by wet plating,
Composite plating was performed under the same conditions as in Example 3.

The composite plated body of the obtained copper plate was used in Example 3
It has properties similar to those obtained in 1., such as film thickness and abrasion resistance, and it was confirmed that the same excellent effects as in the case of dry plating can be obtained even when using coating granules by wet plating. It was

[0053]

[Embodiment 8] Composite plating was carried out under the same conditions as in Embodiment 4 except that diamond powder having a particle size of about 5 μm was used, in which nickel was vapor-deposited on the entire surface by wet plating.

The resulting composite plated aluminum plate had the same excellent properties as those obtained in Example 4,
It was confirmed that the particles coated by the wet plating can be used in this case as well as the particles coated by the dry plating.

[0055]

[Embodiment 9] Particle size of about 0.5 to 1 μm by wet plating
Composite plating was carried out under the same conditions as in Example 5, except that the entire surface of the boron nitride powder of No. 3 was coated with the iron-cobalt alloy.

The obtained ABS resin composite plated body had the same properties as those obtained in Example 5, and the granular body coated by wet plating under these conditions was
It was confirmed that the composite plating of the present invention can be sufficiently used.

[0057]

[Example 10] Particle size of 100 to 200 by wet plating
Composite plating was performed under the same conditions as in Example 6 except that iron was coated on the entire surface of the diamond powder of μm.

The composite plated body of the obtained iron plate was used in Example 6
It has been confirmed that the granules have the same properties as those obtained in 1. and that the wet-coated granules can be sufficiently used for the composite plating of the present invention even under these conditions.

That is, when Examples 7 to 10 were put together, it was confirmed that the coating of the granular material can be used for the composite plating of the present invention regardless of whether dry coating or wet plating is performed.

[Brief description of drawings]

FIG. 1 is a diagram showing a state in which a part of the surface of a granular body is coated with a magnetizing metal.

FIG. 2 is an enlarged view of a granular body in which a part of the surface of the boat is coated with a magnetized metal.

FIG. 3 is a diagram showing a state in which a granular body having a part of the surface coated with a magnetizing metal is placed on a magnetic metal base material and plated.

FIG. 4 is an enlarged view showing a state after the magnetic metal base material is plated using a granular body having a part of the surface coated with a magnetizing metal.

[Explanation of Codes] 1 Boat 2 Adhesive 3 Granular Material 4 Vapor Deposition Equipment 5 Coating Film 6 Magnetic Metal Base Material 7 Plating Film

Claims (4)

[Claims] 1. A sticking agent is applied to a boat, and the particles are dispersed on the boat. The fixing agent is dried, at least a part of the surface of the particles is coated with a magnetic metal by dry plating, and then the fixing agent is removed. A method for coating a granular material, which comprises: 2. A method for coating a granular body, characterized in that the granular body is housed in a boat, and the magnetic substance metal is coated on the granular body by dry plating while rocking the boat. 3. A composite plating method characterized in that at least a part of the surface is coated with a magnetic metal and a granular material is arranged and plated on a magnetic metal base material. 4. A composite plating method characterized in that a granular material coated with a magnetic metal is placed on a magnetic metal substrate and plated.